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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Light-driven C–H activation mediated by 2D transition metal dichalcogenides

C–H bond activation enables the facile synthesis of new chemicals. While C–H activation in short-chain alkanes has been widely investigated, it remains largely unexplored for long-chain organic molecules. Here, we report light-driven C–H activation in complex organic materials mediated by 2D transition metal dichalcogenides (TMDCs) and the resultant solid-state synthesis of luminescent carbon dots in a spatially-resolved fashion. We unravel the efficient H adsorption and a lowered energy barrier of C–C coupling mediated by 2D TMDCs to promote C–H activation and carbon dots synthesis. Our results shed light on 2D materials for C–H activation in organic compounds for applications in organic chemistry, environmental remediation, and photonic materials.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Disentangling plant- and environment-mediated drivers of active rhizosphere bacterial community dynamics during short-term drought

Abstract Mitigating the effects of climate stress on crops is important for global food security. The microbiome associated with plant roots, the rhizobiome, can harbor beneficial microbes that alleviate stress, but the factors influencing their recruitment are unclear. We conducted a greenhouse experiment using field soil with a legacy of growing switchgrass and common bean to investigate the impact of short-term drought severity on the recruitment of active bacterial rhizobiome members. We applied 16S rRNA and 16S rRNA gene sequencing for both crops and metabolite profiling for switchgrass. We included planted and unplanted conditions to distinguish environment- versus plant-mediated rhizobiome drivers. Differences in community structure were observed between crops and between drought and watered and planted and unplanted treatments within crops. Despite crop-specific communities, drought rhizobiome dynamics were similar across the two crops. The presence of a plant more strongly explained the rhizobiome variation in bean (17%) than in switchgrass (3%), with a small effect of plant mediation during drought observed only for the bean rhizobiome. The switchgrass rhizobiome was stable despite changes in rhizosphere metabolite profiles between planted and unplanted treatments. We conclude that rhizobiome responses to short-term drought are crop-specific, with possible decoupling of plant exudation from rhizobiome responses.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Revealing ultrafast proton-transfer-mediated autoionization as a source of low-energy electrons in hydrogen-bonded systems

Ionizing radiation can trigger ultrafast proton transfer, a central mechanism in many chemical and biological functions, that in turn can enable or suppress electron relaxation processes and consequently cause abrupt changes in the reaction pathway. This study combines theory and experiment to probe ultrafast relaxation and dissociation in water dimers following inner- and outer-valence photoionization. By tracking electron and nuclear motion simultaneously, we reveal competing fragmentation pathways that produce low-energy electrons, which are key agents in radiation-induced chemistry, including DNA damage. While low-energy electrons are known to arise via intermolecular Coulombic decay, here we identify a faster relaxation mechanism gated by proton transfer following inner-valence ionization, which we call proton-transfer-mediated autoionization. Occurring within 10 femtoseconds, this process alters fragmentation outcomes, yielding either D 3 O + + OD + or D 2 O + + D 2 O + , depending on the interplay of proton migration and hydrogen back-transfer. Our findings underscore the intricate coupling between electronic and nuclear dynamics in hydrogen-bonded systems and establish proton-transfer-mediated autoionization as a significant pathway for low-energy electron generation.

Atomic and molecular interactions with photons↗
DOE OSTI2023

Circumventing the phonon bottleneck by multiphonon-mediated hot exciton cooling at the nanoscale

Abstract Nonradiative processes govern efficiencies of semiconductor nanocrystal (NC)-based devices. A central process is hot exciton cooling, or the nonradiative relaxation of a highly excited electron/hole pair to form a band-edge exciton. Due to quantum confinement effects, the timescale and mechanism of cooling are not well understood. A mismatch between electronic energy gaps and phonon frequencies has led to the hypothesis of a phonon bottleneck and extremely slow cooling, while enhanced electron-hole interactions have suggested ultrafast cooling. Experimental measurements of the cooling timescale range six orders of magnitude. Here, we develop an atomistic approach to describe phonon-mediated exciton dynamics and simulate cooling in NCs of experimentally relevant sizes. We find that cooling occurs on ~30 fs timescales in CdSe NCs, in agreement with the most recent measurements, and that the phonon bottleneck is circumvented through a cascade of multiphonon-mediated relaxation events. Furthermore, we identify NC handles for tuning the cooling timescale.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Spinon mediation of witness spin dynamics in herbertsmithite

The kagome lattice of spin-1/2 copper atoms in herbertsmithite is conjectured to sustain a quantum spin liquid state with spinon quasiparticles. Ideally, the kagome crystal planes are each separated by a plane of spinless zinc atoms. However, in real crystals, some spin-1/2 copper atoms substitute randomly onto these inter-kagome zinc sites. Here we reconceptualize such ‘impurity’ atoms as quantum witness spins whose dynamics is designed to probe the spin liquid state. We then introduce spin noise spectroscopy to measure the frequency and temperature dependence of witness spin dynamics, demonstrating that their phenomenology is consistent with extensive interactions between witness spins mediated by propagation of spinons through a quantum spin liquid. Ultimately, a sharp transition occurs at around 260 mK, below which the properties of both spin noise and magnetic susceptibility suggest that the witness spins form a spin glass phase. Among the theoretical models considered, we demonstrate that our observations are only consistent with spinon-mediated interactions between witness spins by either a Z 2 or U(1) quantum spin liquid, with the former model more closely matching the data. Our work demonstrates that quantum mechanical witness spins may now conceivably be used as a widely applicable probe of quantum spin liquid physics.

Takahashi, Hiroto [University of Oxford (United Ki↗
DOE OSTI2021

Role of catalytic nitrile decomposition in tricopper complex mediated direct partial oxidation of methane to methanol

Synthetic homogeneous system known to date performing methane to methanol conversion using O 2 as terminal oxidant is unique and based on copper complex with piperazine-based ligand (Cu 3 L in Fig. 1) in a medium of acetonitrile. Prior work have shown that in order to achieve catalytic turnover, hydrogen peroxide is needed to regenerate the active site. We show in this paper that reaction solvent based on organic nitrile decompose concurrently with methane activation and that in the absence of either acetonitrile, Cu complex or hydrogen peroxide, the catalytic turnover does not happen. We show in this manuscript that the direct methane oxidation to methanol might have been mediated by catalytic Radziszewski oxidation between acetonitrile and H 2 O 2 . Additionally we have discovered that in the absence of methane, peroxide mediated acetonitrile decomposition also makes methanol via a background reaction which was hitherto unknown.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Delivered complementation in planta (DCIP) enables measurement of peptide-mediated protein delivery efficiency in plants

Abstract Using a fluorescence complementation assay, Delivered Complementation in Planta (DCIP), we demonstrate cell-penetrating peptide-mediated cytosolic delivery of peptides and recombinant proteins in Nicotiana benthamiana. We show that DCIP enables quantitative measurement of protein delivery efficiency and enables functional screening of cell-penetrating peptides for in-planta protein delivery. Finally, we demonstrate that DCIP detects cell-penetrating peptide-mediated delivery of recombinantly expressed proteins such as mCherry and Lifeact into intact leaves. We also demonstrate delivery of a recombinant plant transcription factor, WUSCHEL (AtWUS), into N. benthamiana. RT-qPCR analysis of AtWUS delivery in Arabidopsis seedlings also suggests delivered WUS can recapitulate transcriptional changes induced by overexpression of AtWUS. Taken together, our findings demonstrate that DCIP offers a new and powerful tool for interrogating cytosolic delivery of proteins in plants and highlights future avenues for engineering plant physiology.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Aqueous-soluble bipyridine cobalt($\tiny{II}$/$\tiny{III}$) complexes act as direct redox mediators in photosystem I-based biophotovoltaic devices

Sustainable energy production is critical for meeting growing worldwide energy demands. Due to its stability and reduction potential, photosystem I (PSI) is attractive as the photosensitizer in biophotovoltaic devices. Herein, we characterize aqueous and organic solvent soluble synthetic bipyridine-based cobalt complexes as redox mediators for PSI-based biophotovoltaics applications. Cobalt-based complexes are not destructive to protein and have appropriate midpoint potentials for electron donation to PSI. We report on PSI stability in organic solvents commonly used in biophotovoltaics. We also show the effects of a mixed organic solvent phase on PSI reduction kinetics, slowing reduction rates approximately 8–38 fold as compared to fully aqueous systems, with implications for dye regeneration rates in PSI-based biophotovoltaics. Further, we show evidence of direct electron transfer from cobalt complexes to PSI. Finally, we report on photocurrent generation from Co mediator-PSI biophotovoltaic devices. Taken together, we discuss the development of novel Co complexes and our ability to fine-tune their characteristics via functional groups and counteranion choice to drive interaction with a biological electron acceptor on multiple levels from redox midpoints, spectral overlap, and solvent requirements, among others. This work suggests that fine-tuning of redox active species for interaction with a biological partner is possible for the creation and improvement of low cost, carbon-neutral energy production in the future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Depolymerization of lignin for biological conversion through sulfonation and a chelator-mediated Fenton reaction

The generating value from lignin through depolymerization and biological conversion to valuable fuels, chemicals, or intermediates has great promise but is limited by several factors including lack of cost-effective depolymerization methods, toxicity within the breakdown products, and low bioconversion of the breakdown products. High yield depolymerization of natural lignins requires cleaving carbon-carbon bonds in addition to ether bonds. To address that need, we report that a chelator-mediated Fenton reaction can efficiently cleave C-C bonds in sulfonated polymers at or near room temperature, and that unwanted repolymerization can be minimized through optimizing reaction conditions. This method was used to depolymerize lignosulfonate from M w = 28,000 g/mol to M w = 800 g/mol. The breakdown products were characterized by SEC, FTIR and NMR and evaluated for bioavailability. The breakdown products are rich in acid, aldehyde, and alcohol functionalities but are largely devoid of aromatics and aliphatic dienes. A panel of nine organisms were tested for the ability to grow on the breakdown products. Growth at a low level was observed for several monocultures on the depolymerized LS in absence of glucose. Much stronger growth was observed in the presence of 0.2% glucose and for one organism we demonstrate doubling of melanin production in the presence of depolymerized LS. The results suggest that this chelator-mediated Fenton method is a promising new approach for biological conversion of lignin into higher value chemicals or intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Catalytically mediated epitaxy of 3D semiconductors on van der Waals substrates

The formation of well-controlled interfaces between materials of different structure and bonding is a key requirement when developing new devices and functionalities. Of particular importance are epitaxial or low defect density interfaces between two-dimensional materials and three-dimensional semiconductors or metals, where an interfacial structure influences electrical conductivity in field effect and optoelectronic devices, charge transfer for spintronics and catalysis, and proximity-induced superconductivity. Epitaxy and hence well-defined interfacial structure has been demonstrated for several metals on van der Waals-bonded substrates. Semiconductor epitaxy on such substrates has been harder to control, for example during chemical vapor deposition of Si and Ge on graphene. Here, we demonstrate a catalytically mediated het-eroepitaxy approach to achieve epitaxial growth of three-dimensional semiconductors such as Ge and Si on van der Waals-bonded materials such as graphene and hexagonal boron nitride. Epitaxy is "transferred" from the substrate to semiconductor nanocrystals via solid metal nano-crystals that readily align on the substrate and catalyze the formation of aligned nuclei of the semiconductor. In situ transmission electron microscopy allows us to elucidate the reaction pathway for this process and to show that solid metal nanocrystals can catalyze semiconductor growth at a significantly lower temperature than direct chemical vapor deposition or deposition mediated by liquid catalyst droplets. We discuss Ge and Si growth as a model system to explore the details of such hetero-interfacing and its applicability to a broader range of materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Effect of a redox-mediating ligand shell on photocatalysis by CdS quantum dots

Semiconductor quantum dots (QDs) are efficient organic photoredox catalysts due to their high extinction coefficients and easily tunable band edge potentials. Despite the majority of the surface being covered by ligands, our understanding of the effect of the ligand shell on organic photocatalysis is limited to steric effects. We hypothesize that we can increase the activity of QD photocatalysts by designing a ligand shell with targeted electronic properties, namely, redox-mediating ligands. Herein, we functionalize our QDs with hole-mediating ferrocene (Fc) derivative ligands and perform a reaction where the slow step is hole transfer from QD to substrate. Surprisingly, we find that a hole-shuttling Fc inhibits catalysis, but confers much greater stability to the catalyst by preventing a build-up of destructive holes. We also find that dynamically bound Fc ligands can promote catalysis by surface exchange and creation of a more permeable ligand shell. Finally, we find that trapping the electron on a ligand dramatically increases the rate of reaction. Furthermore, these results have major implications for understanding the rate-limiting processes for charge transfer from QDs and the role of the ligand shell in modulating it.

Chemistry↗
DOE OSTI2025

Diffusion-mediated passing of molecular species in linear nanopores constrained by orientational alignment

For diffusion-mediated catalytic conversion reactions in materials with narrow linear nanopores, e.g., mesoporous silica MCM-41, a key parameter is the propensity for product species to be able to pass reactant species and thus to efficiently exit the pore. For elongated species, this can require orientational alignment with the pore axis. In this work, we perform benchmark analyses for such solution-phase systems where one of these species is elongated in order to quantify the dependence of this passing propensity, P, on pore diameter and on the rotational diffusion coefficient, Dr, of the elongated species. In particular, we consider the passing of a spherical and an elongated spherocylindrical shaped species in a cylindrical pore in an implicit solvent, where these species cannot overlap. Passing is mediated by diffusive Brownian motion of these species as described by strongly damped Langevin dynamics. We quantify scaling of P for pore width just above the threshold where passing is sterically blocked, and also reveal a significant decrease in P for lower Dr. We also consider the dependence of P on the aspect ratio of the elongated species and obtain an exact result in the limiting regime of large aspect ratio.

Brownian motion↗
DOE OSTI2020

Fc-mediated effector function contributes to the in vivo antiviral effect of an HIV neutralizing antibody

Significance Neutralizing antibodies (NAbs) against HIV-1 are under clinical development. Despite demonstrated antiviral activity when used as treatment in HIV-infected people, the mechanism of action of NAbs remains controversial. Quantification of the relative contribution of Fab-mediated (neutralization of free virus) and Fc-mediated functions such as antibody-dependent cellular cytotoxicity (ADCC), phagocytosis, and complement fixation is essential to develop better therapies. Here, we treated chronically SHIV-infected rhesus macaques with a single dose of NAb VRC07-523LS with or without Fc modifications. Fc function contributes 21% to the antiviral activity of VRC07-523LS with an unmodified Fc region, when compared to NAb with Fc knockout mutations. However, NAbs with improved ADCC function in vitro did not show enhanced antiviral activity in vivo.

Asokan, Mangaiarkarasi↗
DOE OSTI2024

Magnon-mediated qubit coupling determined via dissipation measurements

Controlled interaction between localized and delocalized solid-state spin systems offers a compelling platform for on-chip quantum information processing with quantum spintronics. Hybrid quantum systems (HQSs) of localized nitrogen-vacancy (NV) centers in diamond and delocalized magnon modes in ferrimagnets—systems with naturally commensurate energies—have recently attracted significant attention, especially for interconnecting isolated spin qubits at length-scales far beyond those set by the dipolar coupling. However, despite extensive theoretical efforts, there is a lack of experimental characterization of the magnon-mediated interaction between NV centers, which is necessary to develop such hybrid quantum architectures. Here, we experimentally determine the magnon-mediated NV–NV coupling from the magnon-induced self-energy of NV centers. Our results are quantitatively consistent with a model in which the NV center is coupled to magnons by dipolar interactions. This work provides a versatile tool to characterize HQSs in the absence of strong coupling, informing future efforts to engineer entangled solid-state systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Modification of Wool Fibers via Base/Cationic Detergent Pretreatment and Transglutaminase-mediated Reaction of Keratin

The surface modification of wool fibers is an important part of the textile industry to add functionality and stability to wool products. In this study, we developed a process utilizing a base/cationic surfactant solution pretreatment followed by an enzyme-mediated keratin crosslinking reaction to modify the wool fibers. Changes in water contact angle demonstrated the successful transformation of the hydrophobic wool surface to a more hydrophilic one after soaking in sodium carbonate solution containing hexadecyltrimethylammonium bromide (CTAB). The treated fabrics were further characterized by colorimetry and fluorescent spectrometry. Results showed that the pretreatment increased the yellowness of fabrics and caused some structural changes among certain amino acids, such as tryptophan and cystine. Keratin extracted from coarse wool fibers was further applied on pretreated fabrics through a microbial transglutaminase (mTGase) mediated reaction under mild conditions. Morphological characterization via SEM demonstrated the effective coverage of keratin on the scales of wool. The current method may provide an alternative processing protocol to modify wool fibers and improve the quality and performance of wool products.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Analytic results for scalar-mediated Higgs boson production in association with two jets

Abstract We present compact analytic formulae for all one-loop amplitudes representing the production of a Higgs boson in association with two jets, mediated by a colour triplet scalar particle. Many of the integral coefficients present for scalar mediators are identical to the case when a massive fermion circulates in the loop, reflecting a close relationship between the two theories. The calculation is used to study Higgs boson production in association with two jets in a simplified supersymmetry (SUSY) scenario in which the dominant additional contributions arise from loops of top squarks. The results presented here facilitate an indirect search for top squarks in this channel, by a precision measurement of the corresponding cross section. However, we find that the potential for improved discrimination between the Standard Model and SUSY cases suggested by the pattern of results in the one- and two-jet samples is unlikely to be realized due to the loss in statistical power compared to an inclusive analysis.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

Constraints on dark matter scattering with long lived mediators from observations of the Sun with the Fermi Large Area Telescope

The Sun represents a promising target for indirect dark matter searches, as dark matter particles from the Galactic halo can be gravitationally trapped in its core or in external orbits, and their annihilations can lead to final states with standard model particles that are able to reach the Earth. In this work we have considered a scenario in which dark matter particles can annihilate into pairs of long-lived mediators, which in turn can escape from the Sun and decay into pairs of gamma rays or into the bb̅, τ+τ-, μ+μ- channels, with the production of gamma rays in the final states. All these processes are expected to yield an excess in the energy spectrum of gamma rays towards the Sun. We have therefore analyzed the data collected by the Fermi Large Area Telescope during its first 13.5 years of operation, searching for possible excesses in the solar gamma-ray spectrum. Since no statistically significant excess is found, we have set constraints on the dark matter-nucleon scattering cross sections in both the spin-dependent and spin-independent cases. For all the mediator decay channels explored and for dark matter masses between a few GeV/c 2 and 1 TeV/c 2 , we have found that the upper limits on the spin-dependent and spin-independent cross sections are in the ranges from 10 -45 to 10 -39 cm 2 and from 10 -47 up to 10 -42 cm 2 , respectively.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Solar reflection of dark matter with dark-photon mediators

Abstract We consider the scattering of low-mass halo dark-matter particles in the hot plasma of the Sun, focusing on dark matter that interact with ordinary matter through a dark-photon mediator. The resulting “solar-reflected” dark matter (SRDM) component contains high-velocity particles, which significantly extend the sensitivity of terrestrial direct-detection experiments to sub-MeV dark-matter masses. We use a detailed Monte Carlo simulation to model the propagation and scattering of dark-matter particles in the Sun, including thermal effects, with special emphasis on ultralight dark-photon mediators. We study the properties of the SRDM flux, obtain exclusion limits from various direct-detection experiments, and provide projections for future experiments, focusing especially on those with silicon and xenon targets. We find that proposed future experiments with xenon and silicon targets can probe the entire “freeze-in benchmark”, in which dark matter is coupled to an ultralight dark photon, including dark-matter masses as low as 𝒪(keV). Our simulations and SRDM fluxes are publicly available.

Astronomy & Astrophysics↗